Ethane oligomerization and polymeric chromium catalyst and preparation method thereof

A catalyst, the technology of ethoxycarbonylpyridine chromium halide, is applied in the field of N-N-O tridentate ligand chromium complex catalyst, which can solve the problem of no model compound, limited ethylene oligomerization and polymerization industrial development, active center and mechanism are not confirmed, etc. problem, to achieve the effect of low price

Active Publication Date: 2011-06-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Characterized by analytical means such as NMR, but until now there is still no real model compound
The active center and mechanism of the catalytic reaction have not yet been confirmed, and the active chromium accounts for less than 1%
[0004] However, most of the above-mentioned catalysts are protected or covered by foreign patents, which seriously limits the development of my country's ethylene oligomerization and polymerization industry. It is imminent to research and develop ethylene oligomerization and polymerization catalysts with independent intellectual property rights.

Method used

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  • Ethane oligomerization and polymeric chromium catalyst and preparation method thereof
  • Ethane oligomerization and polymeric chromium catalyst and preparation method thereof
  • Ethane oligomerization and polymeric chromium catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] 1. The preparation of catalyst C1: Chromium tetrahydrofuran chloride (0.372g, 1mmol) and corresponding 6-ester group-2-iminopyridine L1 (0.296g, 1mmol) are added in the Schlenk bottle, and the logical N 2 After three replacements, add treated dichloromethane (10ml), stir at room temperature for 24 hours, add anhydrous diethyl ether after concentration, a green precipitate precipitates, after filtration, vacuum-dry to obtain the complex (0.390g, 0.86mmol), C1 yield: 86%. Elemental Analysis Theoretical Value C 18 h 20 Cl 3 CrN 2 o 2 : C, 47.54; H, 4.43; N, 6.16. Found: C, 47.44; H, 4.60; N, 6.33%. IR(KBr:cm -1 ): 1642; 1587; 1467; 1407; 1381; 1341; 1291; 1217; 1097; 992; 851; 768cm -1 .

[0047] 2. Ethylene polymerization: Dry the 250ml polymerization bottle equipped with a magnetic stirrer at 130°C for 6 hours continuously, vacuumize it while it is hot and use N 2 Air replacement 3 times. Catalyst C1 (2.3 mg, 5 μmol) was added, followed by evacuation and replac...

Embodiment 2

[0049] 1. The preparation of catalyst C1 is the same as in Example 1.

[0050] 2. Ethylene polymerization: Vacuumize a 250 ml stainless steel kettle equipped with a mechanical stirrer and a thermocouple, replace it with nitrogen for 3 times, and then replace it with ethylene for 2 times. After cooling to 25°C, add the toluene solution of catalyst C1 (2.3 mg, 5 μmol) and a certain amount of toluene in sequence, and finally add a certain amount of ethylaluminum dichloride (1mol / L, 5ml) to make Al / Cr=1000, The total volume of toluene was 100 mL. The ethylene pressure was immediately raised to 10 atm and stirred vigorously at 25°C for 30 minutes. After cooling, take out a little reaction solution, neutralize the MAO in it with dilute hydrochloric acid at 0°C, take a small amount of toluene layer, dry it with anhydrous sodium sulfate, and measure the content and distribution of oligomers by gas chromatography. As a result, no oligomers were formed. Pour the remaining reaction so...

Embodiment 3

[0052] 1. The preparation of catalyst C1 is the same as in Example 1.

[0053] 2. Ethylene polymerization: Dry the 250ml polymerization bottle equipped with a magnetic stirrer at 130°C for 6 hours continuously, vacuumize it while it is hot and use N 2 Air replacement 3 times. Catalyst C1 (2.3 mg, 5 μmol) was added, followed by evacuation and replacement with ethylene twice. A certain amount of toluene (29.6ml) was injected with a syringe, and a hexane solution of diethylaluminum chloride (0.375ml) was added. Make Al / Cr = 150, keep the ethylene pressure of 1 atm at 25°C, and stir vigorously for 30 minutes. Add 5% hydrochloric acid ethanol solution to the reaction solution for neutralization, and a white solid precipitates out. But the amount is so small that it cannot be filtered out.

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Abstract

The present invention discloses a series of complex containing 6-ethyl-2-iminobis-phenazopyridine-chromium halide with the formula below, in which R<1>-R<5> can individually select hydrogen, alkyl containing 1-20 carbon atoms, alkaryl, arylalkyl, and halogen, which is represented by X. The present invention also discloses the preparation method for the novel complex, as well as the catalytic compound containing the novel complex and the application thereof to oligomer and polymer of ethane. The preparation of the complex provided by the present invention steps from raw materials with simple structure and low cost, each procedure is easily accomplishable with high yield, the modifiable space of the ligand is relatively large, high polymerization activity is observed in the corresponding catalyst combination, the obtained polymer has lower molecular weight, and the distribution of molecular weight is narrow (compared with the cases reported by previous researches), however, the Tm( DEG C) is above 130, and the obtained polymer is high-linear polyethylene.

Description

Technical field: [0001] The invention relates to a chromium catalyst for ethylene oligomerization and polymerization, in particular to a novel N-N-O tridentate ligand chromium complex catalyst, and its preparation method is used to catalyze ethylene oligomerization and polymerization. Background technique: [0002] As we all know, there are currently two industrialized ethylene polymerization catalyst systems, one is the Ziegler-Natta catalyst, which is a binary system composed of transition metal salts and alkyl metal compounds, and the other is the chromium-based ethylene polymerization catalyst developed by Philips. . According to statistics, 1 / 3 of the world's total ethylene products are produced using chromium-based ethylene polymerization catalysts developed by Philips. Chromium-based catalysts have become the main catalyst system for the preparation of HDPE and LLDPE. Chromium-based catalysts have attracted more and more attention because of their high activity, sim...

Claims

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Application Information

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IPC IPC(8): C07F11/00B01J31/18B01J31/34C08F4/622C07C2/22C08F10/02
Inventor 王文清张文娟于永玲张树李留忠孙文华
Owner CHINA PETROLEUM & CHEM CORP
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